This invention relates to a new catalyst composition useful for initiating and promoting polymerization of .alpha.-olefins and to a polymerization process employing such a catalyst composition.
It is well known that olefins such as ethylene, propylene, and 1-butene in the presence of metallic catalysts, particularly the reaction products of organometallic compounds and transition metal compounds can be polymerized to form substantially linear polymers of relatively high molecular weight. Typically such polymerizations are carried out at relatively low temperatures and pressures.
Among the methods for producing such linear olefin polymers, some of the most widely utilized are those described by Professor Karl Ziegler in U.S. Pat. Nos. 3,113,115 and 3,257,332. In these methods, the catalyst employed is obtained by admixing a compound of a transition metal of Groups IV-B, V-B, VI-B AND VIII of Mendeleeve's Periodic Table of Elements with an organometallic compound. Generally the halides, oxyhalides and alkoxides or esters of titanium, vanadium, and zirconium are the most widely used transition metal compounds. Common examples of the organometallic compounds include the hydride, alkyls and haloalkyls of aluminum, alkylaluminum halides, Grignard reagents, alkali metal aluminum hydrides, alkali metal borohydrides, alkali metal hydrides, alkaline earth metal hydrides and the like. Usually, the polymerization is carried out in a reaction medium comprising an inert organic liquid, e.g., an aliphatic hydrocarbon and the aforementioned catalyst. One or more olefins may be brought into contact with the reaction medium in any suitable manner, and a molecular weight regulator, such as hydrogen, is often added to the reaction vessel in order to control the molecular weight of the polymers. Such polymerization processes are either carried out at slurry polymerization temperatures (i.e., wherein the resulting polymer is not dissolved in the hydrocarbon reaction medium) or at solution polymerization temperatures (i.e., wherein the temperature is high enough to solubilize the polymer in the reaction medium).
Following polymerization, it is common to remove catalyst residues from the polymer by repeatedly treating the polymer with alcohol or other deactivating agents such as an aqueous basic solution. Such catalyst deactivation and/or removal procedures are expensive both in time and material consumed as well as the equipment required to carry out such treatment.
Moreover, most slurry polymerization processes employing the aforementioned known catalyst systems are accompanied by reactor-fouling problems. As a result of such reactor fouling, it is necessary to frequently stop the process to clean the polymerization reactor.
In view of the foregoing problems encountered in the use of conventional Ziegler catalyst, it would be highly desirable to provide a polymerization catalyst which is sufficiently active to eliminate the need for catalyst residue removal and which minimizes reactor fouling problems. In slurry polymerization processes, it would be especially desirable to provide a high efficiency catalyst that would yield a polyolefin powder having an unsettled bulk density of 20-35 pounds per cubic foot.
This has been accomplished by the catalysts disclosed in U.S. Pat. No. 4,244,838 issued to D. E. Gessell, which solid supported catalysts are prepared by
(A) reacting in the presence of a diluent such as n-hexane a mixture of
(1) the reaction product of
(a) an organomagnesium compound such as a dibutyl magnesium; and
(b) at least one of water, carbon dioxide or an organic, oxygen-containing compound such as n-propyl alcohol; and
(2) a transition metal halide such as titanium tetrachloride; and
(B) recovering the solid precipitate such as by decanting; and
(C) washing the solid with a solvent such as n-hexane.
The resultant solid supported catalyst contains sufficient transition metal which, when activated with a suitable activating agent, serves as a polymerization catalyst for .alpha.-olefins. Polymers prepared employing these catalysts have a relatively narrow molecular weight distribution.
The present invention solves the aforementioned problems while providing polymers having a relatively broad molecular weight distribution.